Method of polymerizing oxygen



May 5, 1953 E. J. RYAN METHOD oF POLYMERIZING OXYGEN Filed Feb. 7, 1950 JNVENToR.

,4free/v5! Patented May 5, 1953 STATES TENT OFFIC 5 Claims.

This invention relates to activation of gases and the normally gaseous products formed thereby.

In my parent application, Serial No. 50,199 iiled September 20, 1948, of which the present application is a continuation in part, I have described the activation of several gases, particun larly oxygen and combinations thereof with other gases such as halogen or inert gases such as helium, by subjecting the saine to unusual conditions of exposure to radiant energy, such as ultra violet light in the range of 2,000 to 4,800 angstrom units and a high voltage discharge in the range of 11,000 to 18,000 While maintaining the gas at raised temperatures and pressures of 100 to 200 F. and l0 to 50 lbs. gauge respectively, after which the gas may be further catalytically treated by passing through a catalyst such as sea Water. The gases obtained thereby are activated and appear to be more reactive in their known reactions probably due to formation of higher polymers of such gases and further the Contact with the sea water may impart trace quantities of halogen gas.

I have found that the gases subjected in sequence and at raised temperatures and pressures iirst, to ultra violet light irradiation and then to a high voltage treatment consisting of a corona discharge in the preferred high voltage range of 11,000 to 18,000 and sometimes higher, for ex.- ample at voltages ranging from 5,000 to 50,000, gives substantial polymerization of the gas. In the general Aprior art practices the ozonization of air seldom produces an ozone content exceeding 2%. The gas oxygen, treated according to the present method, is converted to a high concentration of oxygen polymers. Moreover, such polymerization while containing substantial quantities of O3 appear to contain higher polymers of oxygen than Oz.

As further disclosed in my parent application the gas may be given a final catalytic treatment by passing the same through a liquid catalyst comprising a dilute salt solution such as sea water. Such treatment appears to enhance the polymerization and the activity of the gas as an oxidizing agent. And, though a trace quantity of halogen may be present in the gas due to oxidation of halogen salts in the water no free halogen as such is found in the gas, although unmethods.

have further found according to the present invention that such gas can be more highly activated, probably by a higher degree of polymerization and, in part, by imparting a substantial but minor halogen content thereto, such as from .1 to 25% by varying more widely the conditions of polymerization and increasing the halogen content either by addition of halogen to the gas while it is being subjected to radiant energy and high voltage dise-barge under heat and pressure or by increasing the halogen Content of the 'nal catalytic contact solution and by both.

The activated oxygen containing gases hereof, when more highly activated by having a positive halogen content provide a wider field of utility by reason of greater activity. Thus, for example the gas oxygen, in more highly polymeric form and activated by a content .of halogen, becomes a more active oxidizing agent.

I am not aware at this time as to the exact nature of the reactions which take place in the several stages of treatment but it appears that the gas after silbiecting t0 ultra violet light and high voltage discharge at raised temperatures and pressures appears to contain heretofore unrecognized hgher polymers and possibly reaction products thereof with halogen, when halogen is present.

As described in my parent application gas after polymerization by ultra viole-t light and nigh voltage discharge may be given a nal catalytic treatment with an aqueous solution containing halogen salts in minor `proportions as well as suspended free halogen. Such solutions as described therein `for catalyst treatment were substantially dilute containing no more than about 3% of salt as will be normal in ordinary sea water. The gas so treated contains traces, if any, of halogen, the efeot of such treatment being to more highly activate the gas. When treated however, with a more concentrated halogen solution as described hereinbelow a substantial halogen content is imparted to the gas Whether or not halogen is initially present during the polymerization.

In accordance with the present invention oxygen gas alone, or mixed with a generally inert type gas such as helium, or an activating gas such as chlorine, fluorine, bromine or iine sus.- pensions of vaporized iodine, is first preheated to a temperature exceeding 100 F., generally 100 to 300 F'. However, the higher temperature appears to tend to a higher degree of polymerization for gases other than'diiygen .So that temperatures as high as 800 F. may be used in some 3 instances, operation in the range of 100 to 300 F. for any of the gases being most practical.

The activation of the gas in the several stages of treatment herein is carried out at raised pres- It is found, that a final catalytic treatment with an aqueous halogen solution increases the degree of activation and possibly changes the degree of polymerization. It is probable that sures, such raised pressures at least as high as 5 where the aqueous halogen containing solution is lbs. gauge in the apparatus shown will produce a dilute solution of halogen, very little if any some activation. A pressure of from 10 to 100 halogen is added to the gas and the action may lbs. gauge is practical for small quantity installabe a mere change in the degree of polymerizations of moderate size to produce gas of moderate tion. However, where the aqueous solution is activity, and for larger installations where higher l0 saturated with respect to elemental halogen or pressures are tolerable by the construction therea salt thereof a positive content of halogen is imof, higher pressures may be used and pressures parted to the gas which is slightly variable with such as about 1,000 lbs. per sq. in. are a practical the degree of oxidation of the halogen salt, if limit. It will be understood that higher polymers such is used. While it is noted that a concentend to be more readily formed at higher prestrated aqueous solution of halogen catalyst does sures so that pressures in the range of 10 lbs. to impart a positive halogen content to the gas, 10,000 atmospheres or higher may be used in apsuch halogen may be present as a halogenated paratus constructed suiciently rugged to withproduct of the polymer, free halogen or polystand such pressures. merized halogen, the exact character of the hal- In the iirst stage the gas, as pointed out in ogen being unknown. my parent application is subjected to ultra violet Thus as the catalytic solutions with which the light. The light is generated preferably in the gas may be continuously treated after substantial ultra violet wave length higher than 2000 and I polymerization in earlier stages, I use a dilute have found that ultra violet light in the range solution of halogen in water, where a lesser deof 2300 to 2900 angstrom units is preferable but grec of activity is to be imparted and in which for certain oxygen gas mixtures the wave not more than trace quantities of halogen, if length may range up to 4800. The gasV is then any, would appear in the gas. Such dilute solupassed under these high temperature and prestion may be an aqueous solution of 1 to 4% of sure conditions in contact with a high voltage elemental halogen or a water soluble salt thereof corona discharge. Some polymerization is efdissolved in water. Where a positive halogen fected at a voltage discharge as low as 5,000 volts, content is to be imparted to the gas the aqueous and higher voltages tend to increase the degree solution will contain at least 25% and preferof polymerization, but I prefer as a practical opably will be completely'saturated with elemental erating range a voltage discharge from 11,000 to halogen or a Water soluble salt thereof, based on 50,000 volts but considerably higher voltages may the quantity in which the particular halogen be used. The current used may be direct or alwill dissolve in the Water. Preferably for imternating and is held low enough to prevent parting a halogen content a fully saturated solusparking, a current of 1 to 10 amperes being tion is used and even an excess of the salt or eleusually applied. l mental halogen which may be under pressure is The gas as obtained from the high voltage dis- 4o suspended in the solution to obtain a complete charge stage is activated and shows distinct saturation or super saturation of the solution properties as compared to the 'gas originally supwith the halogen material. plied to the apparatus. However, considerably The aqueous halogen containing catalyst congreater activity is imparted to gas at this stage sists of a solution in water of halogen either as if the oxygen gas is simultaneously passed ,5 pure elemental halogen dissolved in Water, or a through the apparatus mixed with halogen. The Water soluble inorganic halogen ysalt dissolved in quantity of halogen put through the apparatus water. The halogen may be either elemental together With oxygen gas to be activated will halogen or soluble inorganic salts thereof, such Vary with the degree of activity to be imparted as sodium, potassium, lithium, magnesium, barias well as the use of the gas. Where a large exum, strontium or calcium, halides, halates, halcess of halogen is undesirable in view of the proo ites, hypo-halites, or oxy-halides. Specic exposed use of the gas, no halogen will be supplied amples of an inorganic halogen salt or element initially in the early-stages of treatment of the are sodium chloride, sodium bromide, sodium gas. Where such halogen is used it will be supfluoride, sodium iodide, free elemental iodine, plied in desired quantity ranging from a trace ,5 free elemental chlorine, free elemental bromine, up to 25% of the gas being polymerized by the D free elemental uorine, sodium hypo-iodite, soultra Violet and high voltage ``discharge treatdium hypo-fluorite, potassium tri-iodide, potas- `ments. As indicated thegas evolved from the slum hypo-chlorite, potassium bromate, sodium high voltage treatment has substantial activity, periodate, sodium acid fluoride, lithium periodate, probably due to substantial polymerization havsodium hypo-chlorite, chlorine di-oxide, calcium ing taken place and is useful in this state as an iodide, barium chloride, strontium chlorate or activated or halogen activated gas. Y magnesium chloride. Mixtures of such halogen The following table sets forth preferred opermaterials in many instances are desirably used. ating ranges for particular gases: Other substantially inert salts may be used in n. hier: gaat Das Oxyerxctical Oper. Range l0-1,000 10-300 2, 30D-2, 900 5,000-50,000

Preferred Oper. Range 10-40 100-175 2, 30D-2, 900 14, 000-50, 000 Oxygclilegbegnnenge 104,000 10o-300 2, 30o-2, 90o sooo-50,000

Preferred Oper. Range 10-40 100-175` 2, 3D0-2, 900 14,000-16,000 Oxygen, and Chlorine, 10%:

Practical Oper. Range l0l,000 1D0-300 2, BOO-2, 900 5, 000-50, 000

Preferred oper. Range 1li-coo. 10o-175 a300-2,900 14, ooo-16, ooo

the catalyst solution primarily to raise the grave ity of the halogen containing liquid to give optie mum Washing contact with the gas polymer passed therethrough and also to give improved solubility eiects of the halogen. Such inert salts as the soluble sulphates are suitable and the liqf uid in which the halogen is dissolved may be such as already have a natural halogen content as Well as lesscr quantities of other salts, for eX- ample natural halogen-containing brines including ordinary sea Water.

It will be understood that sea Water when used will either he further fortilied with the halogen to substantial saturation for maximum activity or used without further halogen addition Where ordinary activity is desired. Such quantity as normally contained in sea Water, about 21/2 to 3% suffices for activating the gas Without imparting a substantial halogen content thereto. However, for purposes of more highly activating the gas and to impart halogen thereto sea water may be used as a base liquid for further saturation with the halogen material.

The through-put of the gas is variable With the size of the apparatus and the degree of polymerization to be effected. For example in an apparatus wherein each of the units has the capacity of about one cubic foot, the gas will be passed therethrough at a rate of from about .25 to l liters of gas at which rate it is also bubblod through a liter of liquid catalyst.

For further description of the production of active gas reference is made to the drawings herewith:

The single figure shows a supply of gas in one or more individual containers, I0, I2. Id, I6 and Ill labeled therein oxygen, helium, chlorine or other halogen gas. The gases mentioned above to be treated Will be supplied from one of such containers through -a line 20, controlled by valves 22 to a manifold 24 which joins by a T 21 into a common outlet pipe line 2S Where gases either singly or in admixture may be supplied to a suitable heating unit 30 which may be a source of infra-red rays for heating, contained in a press-ure resistant receptacle 25. The infra-red ray lamp 30 is heated by a suitable electrical circuit supplied from a main line 33 through a switch 36 and lines 32 controlled in quantity by a rheostat 34. The preheating chamber 2B is `Sllllplied With a pressure gauge 4:0 and thermometer 42 for adequate control of the pressure and temperature of the gases passed therethrough. The receptacle 26 discharges gas through a pipe line 44 having suitably mounted therein a pressure regulating valve l5 for further control of the pressure supplied to the pipe line 43 for further treatment.

The gas as controlled by valve 49 is lead through a pipe line d1 into a pressure resistant chamber 50 wherein are mounted one or more sources of ultra violet light 52 energized through electrical conduits 54 in circuit with the secondary of a transformer 5E Whose primary side is electrically activated through rheostat 51 and a switch 58 conducting electrical current from the supply lines 38. The gas from the ultra violet light treating chamber 50 discharges through the pipe line 60 controlled by valve 62 and thence is supplied through a line 66 controlled by a valve 68 to a high voltage discharge chamber 54. The high voltage discharge is effected as the corona type through several electrodes 'l0 and 12 illustrated diagrammatically as connected to the secondary of a transformer 14. The primary side is activated by current owing through lines 18 s, controlled by rheostat l and .switch all connects ed to power in ,lines .38. The upper ond of the receptacle S4 is provided with a Elo-o lino BZ controlled by valve 8.4 terminating a T I lttlos 86 which can communicate with the duid oorltainer d by opening valve 8B and with a pipo lino 50 by opening intermediate volvo Si therein..

The fluid container 90 contains a T rittlus 94 providing branch lino 96 containing valve 9 3 through which huid can be received from ultra violet light chamber 5D and/or electrical discharge chamber 64 by suitable manipulation o their valves t2 and 6.8 respectively Similarlyt by closure of volvo 139 and opening valve 88, eos from line 48 may be passed directly to a high voltage discharge chamber 54 and thence into lino 96, thus Icy-passing the ultra violet light chambor. Clas from either or preferably both of the fluid containers .S0 or 95 passing through the T tting 94 is then directed through a pipe |00 submerged in liquid catalyst solution 1.02 maintained at a level sumoiont to allow bubbling Contact of the eas passed through pipo itil, eas is thon emitted through pino lllli .as activated ses hereof suitably Controlled by volvo H3 which may be of the pressure reducing typo, The catalyst is supplied to tank 19.2 by boing flrot mixed as a solution or slurry in a small mixing tank H0 and thence passed luto the catalyst tank through pipe l!! controlled by volvo H2. The catalyst tank i021 also has lttod in tho bottom thereof the drain pipo lill controlled by valve dit. As thus shown. any O f the several sesos or mixtures thereof may bo rst preheated and Supplied under suitable pressure to a source of ultra violet light and then to a high voltage discharge or either of thom and lnally t0 contact Whllo under pressure with an aqueous catalyst.-

As. disclosed herein when the temperature rouge is below the boiling point of water the catalyst solvent normally is not subject to substantial vaoorization. When tho `eas is heated above the boiling point of the catalyst solvent, the catalyst tank |02 may be iackotod for maintaining the temperature below tho boiling point by bassins cooling water around the catalyst tank. As dosoribed herein the gas after polymerization may often be directly used Without `further catalytic contact, in which caso the catalyst chamber may be omitted entirely or the apparatus as shown may be used with the modiiioatlon that no catalys-t will be placed in the tank lil?,

The following examples illustrate the practice of this invention:

Example 1.--Qxyson obtained from a tank of pure compressed .Oxygen s passed at the rate of li/z liters por minuto through o preheatine chambor wherein it is heated to 150" F. and thence to a chamber of approximately l cu. it. content containing a bank of ultra violet lamps radiating light at. `2%.50 ouest-rom units and at a pressure of 45 lbs. gauge. It was then passed through a high voltage corona discharge unit mounted in a pressure type tank as shown in the drawings herewith, maintained at a voltage discharge of 15,000 Volts, the arrangement of the apparatus being such that the gases pass over the surface of the highly charged light emanating and electrical discharging units. This gas obviously contains polymers at least as high as O3 but may contain substantial quantities of other polymers.

Example II.-Oxygen is passed from a pure oxygen tank at a temperature of F. and a pressure of 40 lbs. gauge through the ultra violet light chamber of the drawing herewith emitting light at -wave lengthof 2500 angstrom units and thence through a high voltage corona discharge maintained at a discharge voltage of 15,000 volts andthen bubbled through a catalyst consisting of ordinary'sea water containing 3% of salt, ordinary sodium chloride and other constituent salts normally present in sea Water. In the apparatus used the treating chambers had a capacity each of about 1 cu. ft. and the gas Was passed therethrough at a rate of 11/2 liters per minute.` -The gas evolved Was an activated oxygen gas having a characteristic odor totally distinct from ozone, the gas easily supportedcombustion, the gas could be liquied under pressure and showed various evidences of Aactivity higher than the original oxygen. An absorption band spectra ofv the gas showed absorptionsfin the range of 3400 to 3500 angstrom units indicating that the gas contained components other than ozone or pure oxygen.

Eample IIL-Oxygen gas as in Example II was passed through the apparatus under the same conditions at a rate of 11/2 liters per minute and nally through a catalyst Which was a saturated solution of sodium hypochlorite in sea Water. This gas had a slightly more pungent odor and also showed an absorption band absorption in the range of 3400 to 3500 angstrom units and combination tests showed presence of a slight quantity of halogen which isprobably present as a chlorine oxide. The gas is so highly activated that it very rapidly supports combustion, for example steel Wire wool burns completely and almost explosively in an atmosphere of this gas.

Example IV.-In another experiment exactly along the lines of Example III a saturated solution of sodium chloride -in sea-water was substituted as the catalyst and the gas presumably containing a trace of free or combined fluorine supported the combustion of ordinary glass. The gas of these examples has a characteristic odor completely distinct from either halogen or ozone.

Example V.-Oxygen gas as in Example II was mixed with a helium gas and passed through the apparatus and thence through a catalyst cornprising ordinary sea water. The gas had the same characteristic odor as the gas of Example I and was more highly activated than ordinary Eample VI.-A mixture of oxygen with chlorine by volume was passed through the apparatus, at a pressure of 500 lbs. per square inch, gauge, at a temperature 'of 200 F. being first subjected to ultra violet light at a Wave length of 2500 angstrom units and then through a high voltage discharge maintainedvat 100,000 volts. The gas vwas found to be more active in typical oxidation reaction than either chlorine or ozone.

Example VIL-A gas prepared as in Example VI except that the catalyst was concentrated sea water solution of sodium fluoride was found to easily burn glass and showed otherr evidence of being an extremely active oxidizing agent.

The gas hereof with the increased activity and apparent content of higher polymeric forms activated in some cases to a greater or lesser de-r gree by a halogen content improves the utility of these gases alone or admixed.

Various modifications will occur to those skilled in the art and it is intended' that the examples set forth be regarded as exemplary and not limiting except as dened in the claims appended hereto.

I claim:

' l1. The method of polymerizing oxygen gas comprising preheating the gas to a temperature in the range of '100 to 800 F. and compressing the gas to a pressure in the range of 10 to 100 lbs. per sq. in. gauge,A irradiating the gas with ultra violet light in the wave length of 2,000 to 4,800 A. U. while maintaining said temperature and pressure and then subjecting the gas'under the same conditions of temperature and pressure to a high voltage corona discharge in the range of 11,000 to 18,000 volts.

2. The method as dened in claim 1 wherein the oxygen gas is mixed with an inert gas prior to polymerizing the same.

3. The method as defined in claim 1 wherein the oxygen gas is mixed with halogen prior to polymerizing' the same. 4. The method as defined in claim 1 wherein the polymerized oxygen containing gas is further treated by passing the same through an aqueous solution of a halogen substance selected from the group consisting of elementary halogen and water soluble halogen salts.

5. The method as defined in claim 1 wherein the polymerized oxygen containing gas is passed through a dilute aqueous solution of a halogen substance selected from the group consisting of elementary halogen and water soluble halogen salts.

6. The method as defined in claim 1 wherein the polymerized oxygen containing gas is passed through a concentrated aqueous solution of a halogen substance selected from the group consisting of elementary halogen and water soluble halogen salts.

EDMUND J. RYAN.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 450,404 Dittrich Apr. '14, 1891 829,875 Lovejoy Aug. 28, 1906 2,134,206 Roberts Oct. 25, 1938 OTHER REFERENCES Vosmaer, Ozone, 1916, pp. 2, 3, 4 and 6. 

1. THE METHOD OF POLYMERIZING OXYGEN GAS COMPRISING PREHEATING THE GAS TO A TEMPERATURE IN THE RANGE OF 100 TO 800* F. AND COMPRISING THE GAS TO A PRESSURE IN THE RANGE OF 10 TO 100 LBS. PER SQ. IN. GAUGE, IRRADIATING THE GAS WITH ULTRA VIOLET LIGHT IN THE WAVE LENGTH OF 2,000 TO 4,800 A. U. WHILE MAINTAINING SAID TEMPERATURE AND PRESSURE AND THEN SUBJECTING THE GAS UNDER THE SAME CONDITIONS OF TEMPERATURE AND PRESSURE TO A HIGH VOLTAGE CORONA DISCHARGE IN THE RANGE OF 11,000 TO 18,000 VOLTS. 